US5688626A - Gamut toner aggregation processes - Google Patents
Gamut toner aggregation processes Download PDFInfo
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- US5688626A US5688626A US08/628,062 US62806296A US5688626A US 5688626 A US5688626 A US 5688626A US 62806296 A US62806296 A US 62806296A US 5688626 A US5688626 A US 5688626A
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/097—Plasticisers; Charge controlling agents
- G03G9/09733—Organic compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/0802—Preparation methods
- G03G9/0804—Preparation methods whereby the components are brought together in a liquid dispersing medium
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- G03G9/00—Developers
- G03G9/08—Developers with toner particles
- G03G9/0802—Preparation methods
- G03G9/0815—Post-treatment
Definitions
- the present invention is generally directed to toner processes, and more specifically, to aggregation and coalescence processes for the preparation of toner compositions.
- the present invention is directed to the economical in situ chemical preparation of toners without the utilization of the known pulverization and/or classification methods, and wherein in embodiments a combination of a set of color toners, which have a wide color gamut and excellent projection efficiency, are provided and which toners possess in embodiments substantially similar, or the same triboelectrical charging characteristics without the aid of external additives.
- the toners prepared possess, for example, an average volume diameter of from about 1 to about 25, and preferably from 2 to about 10 microns, and a narrow GSD (geometric standard deviation) of, for example, from about 1.16 to about 1.26 as measured on the Coulter Counter.
- the resulting toners can be selected for known electrophotographic imaging processes, printing processes, including color processes, and lithography.
- the present invention enables toners with similar triboelectric charging values, and wherein toner surface additives can be avoided or minimized, and wherein the surfactant within which the toner pigment for each toner is dispersed in the same surfactant type, that is a nonionic surfactant, like those illustrated herein including a sulfonal preferred surfactant available from Air Products as Surfynol 104, Surfynol 104 family, and Surfynol GA, and other similar nonionic surfactants containing aliphatic hydroxy groups.
- a nonionic surfactant like those illustrated herein including a sulfonal preferred surfactant available from Air Products as Surfynol 104, Surfynol 104 family, and Surfynol GA, and other similar nonionic surfactants containing aliphatic hydroxy groups.
- the surfactant selected for the pigment dispersion in embodiments of the present invention is water soluble, and thus can be easily removed by washing with water, in contrast to, for example, prior art surfactants like polyvinyl alcohol which bind to the pigment and are not readily removable. Furthermore, the surfactant selected also enables a stable pigment dispersion in which the pigment particles are of a size of from about 60 to about 100 nanometers, thereby enabling the pigment to be easily dispersed in latex particles. Moreover, in embodiments of the present invention.
- the toners obtained comprised of resin and pigment, such as four toners each with different pigments, in each instance possess the same triboelectric charging characteristics even though different pigments are selected for each toner, and different concentrations of pigments may be present, and such characteristics are of importance with respect to the generation of full process color copies, such as the generation of developed colored images in the Xerox Corporation 5775.
- toners Numerous processes are known for the preparation of toners, such as, for example, conventional processes wherein a resin is melt kneaded or extruded with a pigment, micronized and pulverized to provide toner particles with an average volume particle diameter of from about 9 microns to about 20 microns and with broad geometric size distribution of from about 1.3 to about 1.7.
- a resin melt kneaded or extruded with a pigment, micronized and pulverized to provide toner particles with an average volume particle diameter of from about 9 microns to about 20 microns and with broad geometric size distribution of from about 1.3 to about 1.7.
- the toners have to be further classified leading to low toner yields.
- toner yields range from about 70 percent to about 85 percent after classification. Additionally, during the preparation of smaller sized toners with particle sizes of from about 7 microns to about 11 microns, lower toner yields can be obtained after classification, such as from about 50 percent to about 70 percent; particle sizes of 4 to 7 microns leads to even lower yields such as 40 to 55 percent.
- small average particle sizes of, for example, from about 3 microns to about 9 microns, and preferably 5 microns, are attained without resorting to classification processes, and wherein narrow geometric size distributions are attained, such as from about 1.16 to about 1.30, and preferably from about 1.16 to about 1.25.
- High toner yields are also attained, such as from about 90 percent to about 96 percent, in embodiments of the present invention.
- small particle size toners of from about 3 microns to about 7 microns can be economically prepared in high yields, such as from about 90 percent to about 96 percent by weight based on the weight of all the toner material ingredients, such as toner resin and pigment.
- Emulsion/aggregation processes for the preparation of toners are illustrated in a number of Xerox Corporation patents, the disclosures of which are totally incorporated herein by reference, such as U.S. Pat. Nos. 5,290,654, 5,278,020, 5,308,734, 5,346,797, 5,370,963, 5,344,738, 5,403,693, 5,418,108, 5,364,729, and 5,346,797.
- a set of black and colored toner compositions which are prepared from aqueous predispersed pigments comprised of finely grounded pigment particles stabilized by nonionic surfactants, such as Surfynol 104 GA, and in embodiments other nonionic surfactants containing aliphatic hydroxy groups.
- Pigments stabilized by the preferred Surfynol surfactants also exhibit extended dispersion stability or shelf life.
- Wide toner color gamuts are readily obtainable with the processes of the present invention regardless of the form of the pigment used, for example dry, wet cake or water dispersions based.
- Projection efficiency is essentially a measure of the amount of light transmitted and a measure of the true shade of the color that is transmitted. The higher the number the better is the projection efficiency. Therefore, the pigment size can be a very important factor in projection efficiency in that the larger the pigment particle size, the less desirable is the light scattering when the pigment is fused and projected on a transparency. Since emulsion aggregation involves aggregation of both, submicron latex and pigment particles into toner size particles, where the growth in particle size is, for example, from submicron to about 3 to about 10 microns there could be a tendency toward a reduction in the projection efficiency, that is, for example, the pigment dispersion does not improve during the process.
- the pigment is further attrited in the melt mixing process and hence the projection efficiency improves.
- the projection efficiency it can be of importance to utilize in emulsion aggregation coalescence in situ process pigments of a small size as indicated herein, and wherein, for example, the projection efficiency, therefore, is primarily a function of pigment particle size, and is dependent on the type of surfactant used to disperse the pigment, providing pigment stability is exhibited.
- the surfactants or the grinding aids selected are custom tailored for each pigment to provide superior pigment stability.
- the surfactant, such as polyvinyl alcohol, or the pigment grinding aids are grafted on to the pigment and cannot easily be removed by washing with water, thus the pigment particles evidence very little to no charging.
- nonionic surfactants such as Surfynols, which are completely water miscible, and the like are selected
- these surfactants are readily removable when washed with water, and there results toners with similar triboelectrical characteristics.
- each toner is prepared by an aggregation/coalescence process comprised of (i) utilization of pigment dispersion comprised of pigment, dispersed or ground in a water soluble nonionic surfactant comprised of the Surfynols; (ii) preparing a pigment mixture of (i) in water, cationic surfactant and other known optional additives by shearing, microfluidizing or ultrasonifying; (iii) shearing the pigment mixture of (ii) with a latex mixture comprised of a polymer resin, anionic surfactant and nonionic surfactant thereby causing a flocculation of the latex particles with pigment particles, which on further stirring allows for the formation of electrostatically stable aggregates of from about 0.5 to about 10 microns in volume diameter as measured by the Coulter
- Combination, gamut, or set refers, in embodiments of the present invention, to separate toners that are not mixed together, rather each toner exists as a separate composition and each toner is incorporated into separate housings containing carrier in a xerographic machine, such as the Xerox Corporation 5775.
- a xerographic machine such as the Xerox Corporation 5775.
- the cyan toner is present in one developer housing
- the magenta toner is present in a second separate developer housing
- the yellow toner is present in a third separate developer housing
- the black toner is present in a fourth separate developer housing
- each developer housing includes therein carrier particles such as those particles comprised of a core with a coating thereover.
- toner combinations are prepared as illustrated herein by emulsion/aggregation/coalesence methods, and wherein the pigment for each toner is dispersed in a nonionic surfactant or grinding aids, such as the Surfynols, thereby permitting the surfactant to be easily removed by washing with water and resulting in toners with similar charging behavior independent of the pigment type selected.
- a nonionic surfactant or grinding aids such as the Surfynols
- the similar toner charging behavior is observed upon removal of the surfactants selected for the processes of the present invention, including in embodiments the surfactants selected for the preparation of the latex, the pigment surfactants or grinding aids, and the surfactant used to stabilize the aggregates.
- a process for the preparation of a combination of toner compositions with an average particle volume diameter of from between about I to about 20 microns, and preferably from about 1 to about 7 microns, and with a narrow GSD of from about 1.2 to about 1.3 and preferably from about 1.16 to about 1.25 as measured by a Coulter Counter.
- each toner being comprised of a composite toner of polymeric resin with pigment and optional additives in high yields of from about 85 percent to about 98 percent by weight of toner without resorting to classification.
- toner compositions with low fusing temperatures of from about 110° C. to about 150° C. and with excellent blocking characteristics at from about 50° C. to about 60° C.
- toner compositions with a high projection efficiency such as from about 75 to about 95 percent efficiency as measured by the Match Scan II spectrophotometer available from Milton-Roy.
- toner compositions which result in minimal, low or no paper curl.
- Another object of the present invention resides in processes for the preparation of small sized toner particles with narrow GSDs, and excellent pigment dispersion by the aggregation of latex particles with pigment particles dispersed in water and a surfactant, and wherein the aggregated particles of toner size can then be caused to coalesce by, for example, heating.
- some factors of interest with respect to controlling particle size and particle size distribution include the concentration of the surfactant used for the pigment dispersion, the concentration of the resin component like acrylic acid in the latex, the temperature of coalescence, and the time of coalescence.
- toners enabling an entire range, or an entire series of colors, such as reds, blues, greens, browns, yellows, pinks, violets, mixtures thereof of colors, and the like, and variations thereof like from light red to dark red and the reds therebetween, from light green to dark green and the greens therebetween, from light brown to dark brown and the browns therebetween, from light yellow to dark yellow and the yellows therebetween, from light violet to dark violet and the violets therebetween, from light pink to dark pink and the pinks therebetween, and the like.
- colors such as reds, blues, greens, browns, yellows, pinks, violets, mixtures thereof of colors, and the like, and variations thereof like from light red to dark red and the reds therebetween, from light green to dark green and the greens therebetween, from light brown to dark brown and the browns therebetween, from light yellow to dark yellow and the yellows therebetween, from light violet to dark violet and the violets therebetween, from light pink to dark pink and the pinks therebetween, and
- toners with excellent high intensity color resolutions, and which toners possess high light transmission allowing about 70 to about 98 percent of the transmitted light passing through a fused image on a transparency to reach the screen from an overhead projector.
- water soluble surfactants such as Surfynol
- each toner can be of a preselected size, such as from about 1 to about 10 microns in volume average diameter, and with narrow GSD by the aggregation of latex or emulsion particles, which aggregation can be accomplished with stirring at a temperature in excess of 25° C., and below about the Tg of the toner resin, for example at 50° C., followed by addition of further stabilizer, for example anionic surfactant, followed by heating the formed aggregates above about the resin Tg to allow for coalescence; an essentially three step process of blending, aggregation and coalescence; and which process can in embodiments be completed in 8 or less hours.
- the emulsion/aggregation process is illustrated in U.S. Pat. Nos. 5,403,693 and 5,364,729.
- the process can comprise dispersing pigment particles in a water/cationic surfactant mixture using a microfluidizer; blending the dispersion with a latex using a SD41 mixer, which allows continuous pumping and shearing at high speeds, which is selected to break initially formed flocks or flocs, thus allowing controlled growth of the particles and improved particle size distribution.
- the pigment/latex blend is then transferred into a kettle equipped with a mechanical stirrer and a temperature probe, and heated up to 45° C. or 50° C. to perform the aggregation.
- Extra anionic surfactant can be added to stabilize the aggregates during the coalescence step.
- the resulting aggregated particles are heated 20° to 50° C. above their polymer Tg to permit coalescence, and the resulting particles are filtered and washed with water to remove the surfactants.
- the toner particles can then be dried in a freeze dryer, spray dryer, or fluid bed dryer.
- Another object of the invention is the provision of toners with excellent triboelectric characteristics, acceptable admix values of, for example, from about 15 to about 60 seconds, wide color gamut, high gloss, excellent projection efficiency, and to provide toner particles having similar charging behavior.
- toners and processes thereof are provided.
- processes for the economical direct preparation of a combination of toners and wherein each toner is obtained by flocculation or heterocoagulation and coalescence, and wherein the temperature of aggregation can be utilized to control the final toner particle size, that is average volume diameter.
- the present invention is directed to processes for the preparation of toner compositions which comprise initially attaining or generating a nonionic pigment dispersion, for example an aqueous dispersion mixture of a pigment or pigments, such as carbon SUNSPERSE BLACK® containing REGAL 330®, SUNSPERSE BLUE® containing phthalocyanine, SUNSPERSE RED® containing quinacridone or RHODAMINE BTM, SUNSPERSE YELLOW® containing pigment yellow 17, with Surfynol surfactants or grinding aids, by known dispersion methods, such as attrition, microfluidization, or high speed homogenization.
- a pigment or pigments such as carbon SUNSPERSE BLACK® containing REGAL 330®, SUNSPERSE BLUE® containing phthalocyanine, SUNSPERSE RED® containing quinacridone or RHODAMINE BTM, SUNSPERSE YELLOW® containing pigment yellow 17, with Surfynol
- This pigment dispersion is then introduced into a water/cationic surfactant mixture, such as benzalkonium chloride, and mixed with the latex by utilizing a high shearing device, such as a Brinkmann Polytron, or microfluidizer.
- a water/cationic surfactant mixture such as benzalkonium chloride
- the latex can be comprised of suspended resin particles, such as poly(styrene butadiene) acrylic acid or poly(styrene butylacrylate) acrylic acid, and wherein the particle size of the suspended resin mixture is, for example, from about 0.01 to about 0.5 micron in an aqueous surfactant mixture containing an anionic surfactant, such as sodium dodecylbenzene sulfonate and nonionic surfactant, such as nonylphenol or octylphenol ethoxylate, resulting in a flocculation, or heterocoagulation of the polymer or resin particles with the pigment particles, followed by further stirring of the mixture while heating below about the resin Tg, for example from about 5° to about 15° C., and allowing the formation of electrostatically stabilized aggregates ranging from about 0.5 micron to about 10 microns; followed by the addition of extra stabilizer, such as anionic surfactant, subsequently heating above about the resin Tg, for example from about 5 to about 50°
- Embodiments of the present invention include a process for the preparation of a combination of toner compositions comprised of resin and pigment, and wherein each toner of the combination is prepared as follows:
- step (iv) adding more anionic stabilizer in the amounts of, for example, from about 0.2 to about 3 percent by weight of water to retain the particle size and GSD during step (v);
- the present invention is directed to processes for the preparation of a combination of four toner compositions which comprise (i) preparing a mixture of pigment, such as carbon black like REGAL 330®, HOSTAPERM PINKTM, or PV FAST BLUETM and Yellow 17, reference the Color Index, which are predispersed in a Surfynol nonionic surfactant or grinding aid, and wherein the pigment loading is in the order of from about 2 to about 14 percent by weight of toner, in an aqueous mixture containing a cationic surfactant, such as dialkylbenzene dialkylammonium chloride like SANIZOL B-50TM available from Kao or MIRAPOLTM available from Alkaril Chemicals, and from about 0.5 to about 2 percent by weight of water utilizing a high shearing device such as a Brinkmann Polytron or IKA homogenizer; (ii) adding the aforementioned pigment mixture to an aqueous suspension of resin particles comprised of, for example, poly(stylene glycol,
- step (v) adding additional anionic surfactant or nonionic surfactant in the amount of from 0.5 percent to 5 percent by weight of water to stabilize the aggregates formed in step (iv), heating the resultant electrostatically bound aggregate composite particles at from about 60° C. to about 135° C.
- toner sized particles for a duration of about 60 minutes to about 600 minutes to form toner sized particles of from about 1 micron to about 10 microns in volume average diameter and with a geometric size distribution of from about 1.2 to about 1.3 as measured by the Coulter Counter; and (vi) isolating the toner sized particles by washing, filtering and drying thereby providing toner particles comprised of resin, pigment, and optional additives, such as charge enhancing additives.
- additives to improve the toner flow characteristics and charge additives, if not initially present, to improve charging characteristics may then be added by blending with the formed toner, such additives including AEROSILS® or fumed silicas, metal oxides like tin, titanium and the like, metal salts of fatty acids, like zinc stearate, and which additives are present in various effective amounts, such as from about 0.1 to about 10 percent by weight of the toner.
- additives including AEROSILS® or fumed silicas, metal oxides like tin, titanium and the like, metal salts of fatty acids, like zinc stearate, and which additives are present in various effective amounts, such as from about 0.1 to about 10 percent by weight of the toner.
- pigments utilized in a dry or in the wet cake form are dispersed in water and a surfactant, preferably a cationic or nonionic surfactant using microfluidization equipment, such as, for example, a M-110 microfluidizer, and passing the pigment dispersion from 1 to 10 times through the chamber of the microfluidizer.
- a surfactant preferably a cationic or nonionic surfactant using microfluidization equipment, such as, for example, a M-110 microfluidizer, and passing the pigment dispersion from 1 to 10 times through the chamber of the microfluidizer.
- Illustrative examples of specific resin particles, resins or polymers selected for the process of the present invention include known polymers such as poly(styrene-butadiene), poly(para-methyl styrene-butadiene), poly(meta-methyl styrene-butadiene), poly(alpha-methyl styrene-butadiene), poly(methylmethacrylate-butadiene), poly(ethylmethacrylate-butadiene), poly(propylmethacrylate-butadiene), poly(butylmethacrylate-butadiene), poly(methylacrylate-butadiene), poly(ethylacrylate-butadiene), poly(propylacrylate-butadiene), poly(butylacrylate-butadiene), poly(styrene-isoprene), poly(para-methyl styrene-isoprene), poly(meta-methyl styrene-isopren
- the resin selected which generally can be in embodiments styrene acrylates, styrene butadienes, styrene methacrylates, or polyesters, are present in various effective amounts, such as from about 85 weight percent to about 98 weight percent of the toner, and can be of small average particle size, such as from about 0.01 micron to about 1 micron in average volume diameter as measured by the Brookhaven nanosize particle analyzer.
- Other sizes and effective amounts of resin particles may be selected in embodiments, for example copolymers of poly(styrene butylacrylate acrylic acid) or poly(styrene butadiene acrylic acid) can be selected as the toner resin.
- the resin selected for the process of the present invention is preferably prepared by emulsion polymerization methods, and the monomers utilized in such processes include styrene, acrylates, methacrylates, butadiene, isoprene, and optionally, but preferably acid or basic olefinic monomers, such as acrylic acid, methacrylic acid, acrylamide, methacrylamide, quaternary ammonium halide of dialkyl or trialkyl acrylamides, or methacrylamide, vinylpyridine, vinylpyrrolidone, vinyl-N-methylpyridinium chloride, and the like.
- the acid or basic groups can be present in various effective amounts, such as from about 0.1 to about 10 percent by weight of the polymer resin.
- chain transfer agents for example dodecanethiol, about 1 to about 10 percent, or carbon tetrabromide and the like in effective amounts, such as from about 1 to about 10 percent, can also be selected when preparing the resin particles by emulsion polymerization.
- each toner in an effective amount of, for example, from about 1 to about 25 percent by weight of the toner, and preferably in an amount of from about 1 to about 15 weight percent, that can be selected include those illustrated, for example, in the Color Index, such as carbon black like REGAL 330®; magnetites, such as Mobay magnetites MO8029TM, MO8060TM; Columbian magnetites; MAPICO BLACKSTM and surface treated magnetites; Pfizer magnetites CB4799TM, CB5300TM, CB5600TM, MCX6369TM; Bayer magnetites, BAYFERROX 8600TM, 8610TM; Northern Pigments magnetites, NP-604TM, NP-608TM; Magnox magnetites TMB-100TM, or TMB-104TM; and the like.
- the Color Index such as carbon black like REGAL 330®
- magnetites such as Mobay magnetites MO8029TM, MO8060TM
- Columbian magnetites MAPICO BLACKSTM and surface treated magnetites
- Pfizer magnetites CB
- colored pigments there can be selected cyan, magenta, yellow, red, green, brown, blue or mixtures thereof.
- Specific examples of pigments, reference the Color index, include phthalocyanine HELIOGEN BLUE L6900TM, D6840TM, D7080TM, D7020TM, PYLAM OIL BLUETM, PYLAM OIL YELLOWTM, PIGMENT BLUE 1TM available from Paul Uhlich & Company, Inc., PIGMENT VIOLET 1TM, PIGMENT RED 48TM, LEMON CHROME YELLOW DCC 1026TM, E. D.
- TOLUIDINE REDTM and BON RED CTM available from Dominion Color Corporation, Ltd., Toronto, Ontario, NOVAPERM YELLOW FGLTM, HOSTAPERM PINK ETM from Hoechst, and CINQUASIA MAGENTATM available from E. I. DuPont de Nemours & Company, and the like.
- colored pigments that can be selected are cyan, magenta, or yellow pigments, and mixtures thereof.
- magenta materials that may be selected as pigments include, for example, 2,9-dimethyl-substituted quinacridone and anthraquinone dye identified in the Color Index as Cl 60710, CI Dispersed Red 15, diazo dye identified in the Color Index as Cl 26050, Cl Solvent Red 19, and the like.
- yellow pigments that may be selected are diaryl
- Colored magnetites such as mixtures of MAPICO BLACKTM, and cyan components may also be selected as pigments with the process of the present invention.
- the pigments selected are present in various effective amounts, such as from about 1 weight percent to about 65 weight and preferably from about 2 to about 12 percent, of the toner.
- the cyan pigment can be Pigment Blue 15:3 having a Color Index Constitution Number of 74160
- the magenta pigment can be Pigment Red 81:3 having a Color Index Constitution Number of 45160:3
- the yellow pigment can be Yellow 17 having a Color Index Constitution Number of 21105
- the cyan or blue, the magenta and the yellow pigments are represented by the following formulas ##STR1## wherein each of the pigments are present in an amount of from about 2 to about 25 weight percent based on the weight percent of resin and pigment; wherein each of the pigments are present in an amount of from about 2 to about 15 weight percent based on the weight percent of resin and pigment; wherein each of said cyan, magenta, yellow and black pigments possesses a diameter particle size or agglomerate diameter size of from about 0.01 micron to about 3 microns; wherein each of said cyan, magenta, and yellow pigments is of a particle diameter size or agglomerate diameter size of from about 0.01 micron to about 0.3 micron
- a combination set, or gamut of four color toners each for the development of electrostatic latent images enabling the formation of a full color gamut image
- the four toners are comprised of a cyan toner, a magenta toner, a yellow toner, and a black toner, each of said toners being comprised of resin and pigment
- the pigment for the cyan toner is a ⁇ -copper phthalocyanine
- the pigment for the magenta toner is a xanthene silicomolybdic acid salt of Rhodamine 6G basic dye
- the pigment for the yellow toner is a diazo benzidine
- the pigment for the black toner is carbon black
- a combination of toners wherein the fused image obtained with said toner combination has a Gardner Gloss value of from about 60 to 90 gloss units, wherein from about 70 to about 98 percent of the transmitted light passing through said fused image contained on a transparency reaches a projection screen from an overhead projector; and an
- the toner may also include known charge additives in effective amounts of, for example, from 0.1 to 5 weight percent, such as alkyl pyridinium halides, bisulfates, the charge control additives of U.S. Pat. Nos. 3,944,493; 4,007,293; 4,079,014; 4,394,430 and 4,560,635, which illustrates a toner with a distearyl dimethyl ammonium methyl sulfate charge additive, the disclosures of which are totally incorporated herein by reference, negative charge enhancing additives like aluminum complexes, and the like.
- charge additives in effective amounts of, for example, from 0.1 to 5 weight percent, such as alkyl pyridinium halides, bisulfates, the charge control additives of U.S. Pat. Nos. 3,944,493; 4,007,293; 4,079,014; 4,394,430 and 4,560,635, which illustrates a toner with a distearyl dimethyl ammoni
- surfactants selected for the invention pigment dispersion are as illustrated herein, and more specifically, include water soluble surfactants, such as the Surfynol(s) available from Air Products and Chemical Inc. with aliphatic hydroxy groups, and more specifically, Surfynol 104 and Surfynol GA.
- the Surfynol 104 is, according to Air Products and Chemical Inc., 2,4,7,9-tetramethyl-5 decyne-4,7-diol containing isopropyl alcohol, about 50 parts of the diol and about 50 parts of the isopropyl alcohol, and the Surfynol 104 includes Surfynols 104BC, 104E, 104H, 104 PA.
- the aforementioned 104BC is 2,4,7,9-tetramethyl-5 decyne-4,7-diol containing 2-butoxyethanol
- the 104E is 2,4,7,9-tetramethyl-5 decyne-4,7-diol containing ethylene glycol
- the 104H is 2,4,7,9-tetramethyl-5 decyne-4,7-diol containing ethylene glycol
- the 104PA is 2,4,7,9-tetramethyl-5 decyne-4,7-diol containing isopropyl alcohol.
- the Surfynol GA is comprised of from about 10 to about 35 parts of 2,4,7,9-tetramethyl-5 decyne-4,7-diol, about 22 parts of 1,2 ethanediol, and from about 30 to about 60 parts of alkyarylalkoxylates.
- Surfactants other than the pigment water soluble surfactants, selected in amounts of, for example, 0.1 to about 25 weight percent in embodiments include, for example, nonionic surfactants such as dialkylphenoxypoly(ethyleneoxy) ethanol, available from Rhone-Poulenac as IGEPAL CA-210TM, IGEPAL CA-520TM, IGE PAL CA-720TM, IGEPAL CO-890TM, IGEPAL CO-720TM, IGEPAL CO-290TM, IGEPAL CA-210TM, ANTAROX 890TM and ANTAROX 897TM.
- An effective concentration of the nonionic surfactant is in embodiments, for example from about 0.01 to about 10 percent by weight, and preferably from about 0.1 to about 5 percent by weight of monomers, used to prepare the copolymer resin.
- ionic surfactants include anionic and cationic with examples of anionic suffactants being, for example, sodium dodecylsulfate (SDS), sodium dodecylbenzene sulfonate, sodium dodecylnaphthalene sulfate, dialkyl benzenealkyl, sulfates and sulfonates, abitic acid, available from Aldrich, NEOGEN RTM, NEOGEN SCTM obtained from Kao, and the like.
- SDS sodium dodecylsulfate
- anionic suffactants being, for example, sodium dodecylsulfate (SDS), sodium dodecylbenzene sulfonate, sodium dodecylnaphthalene sulfate, dialkyl benzenealkyl, sulfates and sulfonates, abitic acid, available from Aldrich, NEOGEN RTM, NEOGEN SCTM obtained from Ka
- An effective concentration of the anionic surfactant generally employed is, for example, from about 0.01 to about 10 percent by weight, and preferably from about 0.1 to about 5 percent by weight of monomers used to prepare the copolymer resin particles of the emulsion or latex blend.
- dialkyl benzenealkyl ammonium chloride lauryl trimethyl ammonium chloride
- This surfactant is utilized in various effective amounts, such as for example from about 0.1 percent to about 5 percent by weight, of water.
- the molar ratio of the cationic surfactant used for flocculation to the anionic surfactant used in the latex preparation is in the range of from about 0.5 to 4, and preferably from 0.5 to 2.
- Weight percent throughout also includes parts in embodiments of the present invention.
- Counterionic surfactants are comprised of either anionic or cationic surfactants as illustrated herein and in the amount indicated, thus, when the ionic surfactant of step (i) is an anionic surfactant, the counterionic surfactant is a cationic surfactant.
- Examples of the surfactant, which are added to the aggregated particles to "freeze” or retain particle size, and GSD achieved in the aggregation can be selected from the anionic surfactants such as sodium dodecylbenzene sulfonate, sodium dodecylnaphthalene sulfate, dialkyl benzenealkyl, sulfates and sulfonates, abitic acid, available from Aldrich, NEOGEN RTM, NEOGEN SCTM obtained from Kao, and the like.
- anionic surfactants such as sodium dodecylbenzene sulfonate, sodium dodecylnaphthalene sulfate, dialkyl benzenealkyl, sulfates and sulfonates, abitic acid, available from Aldrich, NEOGEN RTM, NEOGEN SCTM obtained from Kao, and the like.
- nonionic surfactants such as polyvinyl alcohol, polyacrylic acid, methalose, methyl cellulose, ethyl cellulose, propyl cellulose, hydroxy ethyl cellulose, carboxy methyl cellulose, polyoxyethylene cetyl ether, polyoxyethylene lauryl ether, polyoxyethylene octyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene sorbitan monolaurate, polyoxyethylene stearyl ether, polyoxyethylene nonylphenyl ether, dialkylphenoxypoly(ethyleneoxy) ethanol, available from Rhone-Poulenac as IGEPAL CA-210TM, IGEPAL CA-520TM, IGEPAL CA-720TM, IGEPAL CO-890TM, IGEPAL CO-720TM, IGEPAL CO-290TM, IGEPAL CA-210TM, ANTAROX 890TM and ANTAROX 897TM.
- An effective concentration of the anionic or nonionic surfactant generally employed as a "freezing agent" or stabilizing agent is, for example, from about 0.01 to about 10 percent by weight, and preferably from about 0.5 to about 5 percent by weight of the total weight of the aggregates comprised of resin latex, pigment particles, water, ionic and nonionic surfactants mixture.
- additives that can be added to the toner compositions after washing or drying include, for example, metal salts, metal salts of fatty acids, colloidal silicas, mixtures thereof, and the like, which additives are usually present in an amount of from about 0.1 to about 2 weight percent, reference U.S. Pat. Nos. 3,590,000; 3,720,617; 3,655,374 and 3,983,045, the disclosures of which are totally incorporated herein by reference.
- Preferred additives include zinc stearate and AEROSII R972® available from Degussa in amounts of from 0.1 to 2 percent which can be added during the aggregation process or blended into the formed toner product.
- Developer compositions can be prepared by mixing the toners obtained with the processes of the present invention with known carrier particles, including coated carriers, such as steel, ferrites, and the like, reference U.S. Pat. Nos. 4,937,166 and 4,935,326, the disclosures of which are totally incorporated herein by reference, for example from about 2 percent toner concentration to about 8 percent toner concentration.
- Imaging methods are also envisioned with the toners of the present invention, reference for example a number of the patents mentioned herein, and U.S. Pat. No. 4,265,660, the disclosure of which is totally incorporated herein by reference.
- Prior art pigment dispersions often contain the surfactants grafted onto the pigment particle as indicated herein, and this grafting prevents the surfactant from being easily removed with water, if it can be removed.
- E/A emulsion aggregation
- these types of pigment dispersions are employed to prepare pigmented toner particles by emulsion aggregation (E/A) process, there results particles, or toners with nonremovable suffactants.
- E/A emulsion aggregation
- Similar relatively stable toner triboelectrical charging behavior of the invention results primarily from (i) the removal of the surfactants or pigment grinding aids employed in the pigment dispersion, (ii) the removal of anionic (NEOGEN RTM--sodium dodecylbenzene sulfonate), nonionic (ANTAROX CA 897TM) and the cationic (SANIZOL BTM--benzalkonium chloride) surfactants employed in the emulsion aggregation process, (iii) the pigment being buried in the resin particle and, therefore, the complex pigment chemistry does not substantially interfere with the charging performance of the toner particle, unlike the toner particles prepared by melt mix process, and unlike toners prepared with surfactants that bind to the pigment as indicated herein.
- a polymeric or emulsion latex was prepared by the emulsion polymerization of styrene/butylacrylate/acrylic acid (82/18/2 parts) in a nonionic/anionic surfactant solution (3 percent) as follows. 656 Grams of styrene, 144 grams of butyl acrylate, 16 grams of acrylic acid, 28 grams (3.5 percent) of dodecanethiol, and 8 grams of carbon tetrabromide were mixed with 1,100 milliliters of deionized water in which 18 grams of sodium dodecyl benzene sulfonate anionic surfactant (NEOGEN RTM which contains 60 percent of active component), 17.2 grams of polyoxyethylene nonyl phenyl ether--nonionic surfactant (ANTAROX 897TM--70 percent active), and 8 grams of ammonium persulfate initiator were dissolved in 100 grams of water, which was added to the above.
- the emulsion was then polymerized at 70° C. for 6 hours.
- the zeta potential was measured on Pen Kern Inc.
- the Laser Zee Meter was -95 millivolts for this polymeric latex.
- the particle size of the latex as measured on Brookhaven BI-90 Particle Nanosizer was 136 nanometers.
- toner In 120 milliliter glass bottles, 1 gram of toner was added to 24 grams of carrier particles comprised of 65 micron steel particles coated with a mixture of 20 percent by weight of Vulcan carbon black and 80 weight percent of polymethylmethacrylate, coating weight of 1 percent. For each combination of toner and carrier, the above developer mixture was retained in an environmental chamber at either 20 percent relative humidity, 50 percent relative humidity, or at 80 percent relative humidity overnight, about 18 hours. The bottles were then sealed, and the toner and carrier particles were mixed by roll milling for 30 minutes to obtain a stable triboelectric charge. The toner charge was measured using the standard tribo blow-off apparatus.
- Toner charging admix was determined by selecting a developer that had been charged at 50 percent RH, as described above, and adding a further 1 gram of the above prepared uncharged toner. The developer was then further roll milled and examined using a charge spectrograph after 15 seconds, 30 seconds, and 1 minute of mixing. The admix time is the time at which the added uncharged toner has obtained the same charge as the original charged toner.
- BHD 6000 (53 percent solids) SUNSPERSE BLUETM pigment which pigment is comprised of 15:3 copper phthalocyanine pigment, which is dispersed in a mixture of water and in the surfactant Surfynol GA obtained from Air Products, and comprised of from about 10 to about 35 parts of 2,4,7,9-tetramethyl-5 decyne-4,7-diol, about 22 parts of 1,2 ethanediol, and from about 30 to about 60 parts of alkyarylalkoxylates, was dispersed in 240 milliliters of deionized water containing 2.34 grams of alkylbenzyldimethyl ammonium chloride cationic surfactant (SANIZOL BTM) by stirring.
- SANIZOL BTM alkylbenzyldimethyl ammonium chloride cationic surfactant
- This cationic dispersion of the pigment was then simultaneously added with 260 grams of the above prepared Latex A (40 percent solids) containing 2.3 grams of anionic surfactant and 400 grams of water while being homogenized with an IKA G45M probe for 3 minutes at 5,000 rpm. This mixture was then transferred into a reaction kettle and its temperature raised to 50° C. while being stirred. A sample taken after 2.5 hours indicated the particles had a size of 7.3 microns with a GSD of 1.17. 40 Milliliters of 20 percent (W/W) anionic surfactant solution were then added to the aggregates to prevent any further growth, and the temperature of the reactor raised further to 93° C. and held there for 4 hours to complete the coalescence.
- the toner particles were washed with deionized water several times and freeze dried.
- the resulting toner tribo was 14.7 ⁇ C/gram.
- red dispersion pigment which pigment is comprised of 81:3 red pigment which is dispersed in a mixture of water and in the surfactant Surfynol GA obtained from Air Products, were dispersed in 220 milliliters of deionized water containing 2.34 grams of alkylbenzyldimethyl ammonium chloride cationic surfactant (SANIZOL BTM ) by stirring. This cationic dispersion of the pigment was then simultaneously added with 260 grams of the above prepared Latex A (40 percent solids) containing 2.3 grams of anionic surfactant and 350 grams of water while being homogenized with an IKA G45M probe for 3 minutes at 5,000 rpm.
- SANIZOL BTM alkylbenzyldimethyl ammonium chloride cationic surfactant
- Yellow 17 dispersion pigment which pigment is comprised of Yellow 17 pigment which is dispersed in a mixture of water and in the surfactant Surfynol GA obtained from Air Products, were dispersed in 220 milliliters of deionized water containing 2.6 grams of alkylbenzyldimethyl ammonium chloride cationic surfactant (SANIZOL BTM ) by stirring.
- This cationic dispersion of the pigment was than simultaneously added with 260 grams of the above prepared Latex A (40 percent solids) containing 2.3 grams of artionic surfactant and 350 grams of water while being homogenized with an IKA G45M probe for 3 minutes at 5,000 rpm.
- the resulting cationic dispersion of the pigment was then simultaneously added with 260 grams of the above prepared Latex A (40 percent solids) containing 2.3 grams of anionic surfactant and 350 grams of water while being homogenized with an IKA G45M probe for 3 minutes at 5,000 rpm. This mixture was then transferred into a reaction kettle, and its temperature was raised to 50° C. while being stirred. A sample taken from the kettle after 2 hours indicated a tone particle size of 6.7 microns with a GSD of 1.18. 55 Milliliters of 2 percent (W/W) anionic surfactant solution were added to the aggregates to prevent any further growth, and the temperature of the reactor raised further to 93° C. and held there for4 hours to complete the coalescence.
- C represents the cyan toner containing the Surfynol GA surfactant
- Y, M, and K represent the yellow toner, the magenta toner, and the black toner, respectively, and wherein each of these toners, Y, M, and K, do not contain the Surfynol GA surfactant.
- S/BA/AA refers to the toner resin styrene/butylacrylate/acrylic acid (82/18/2).
- each of the toners, cyan (C), yellow (Y), magenta (M), and black (K) contain the Surfynol GA surfactant
- S/BA/AA refers to the toner resin styrene/butylacrylate/acrylic acid (82/18/2). Similar designations are used in Table 3, and wherein the Surfynol GA surfactant is contained in each of the toners and S/IP/AA refers to styrene/isoprene/acrylic acid toner resin.
Abstract
Description
TABLE 1 ______________________________________ In Situ S/BA/AA Toners Pigment C Y M K ______________________________________ Toner Q/M (μC/g) -14.7 -1.7 -3.6 -1.6 ______________________________________
TABLE 2 ______________________________________ In Situ S/BA/AA Toners With GA Pigments - 20% RH Pigment C Y M K ______________________________________ Toner Q/M (μC/g) -14.7 -14.2 -13.5 -12.5 ______________________________________
TABLE 3 ______________________________________ In Situ S/IP/AA Toners with GA Pigments - 20% RH Pigment C Y M ______________________________________ Toner Q/M (μC/g) -42 -33 -31 ______________________________________
Claims (38)
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US08/628,062 US5688626A (en) | 1996-04-08 | 1996-04-08 | Gamut toner aggregation processes |
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US08/628,062 US5688626A (en) | 1996-04-08 | 1996-04-08 | Gamut toner aggregation processes |
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Cited By (14)
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US5998077A (en) * | 1998-06-29 | 1999-12-07 | Xerox Corporation | Coated carrier |
US6066421A (en) * | 1998-10-23 | 2000-05-23 | Julien; Paul C. | Color toner compositions and processes thereof |
US6066422A (en) * | 1998-10-23 | 2000-05-23 | Xerox Corporation | Color toner compositions and processes thereof |
US6562541B2 (en) | 2001-09-24 | 2003-05-13 | Xerox Corporation | Toner processes |
US20060105263A1 (en) * | 2004-11-16 | 2006-05-18 | Xerox Corporation | Toner composition |
US20070025178A1 (en) * | 2005-07-27 | 2007-02-01 | Xerox Corporation | Pigment dispersions and preparation method thereof |
US20070207397A1 (en) * | 2006-03-03 | 2007-09-06 | Xerox Corporation | Toner compositions |
US20070218395A1 (en) * | 2006-03-15 | 2007-09-20 | Xerox Corporation | Toner compositions |
US20080138731A1 (en) * | 2006-11-21 | 2008-06-12 | Xerox Corporation. | Dual pigment toner compositions |
US20090296173A1 (en) * | 2008-05-28 | 2009-12-03 | Xerox Corporation | Method to create spot colors with white and CMYK toner and achieve color consistency |
US20090325097A1 (en) * | 2008-06-25 | 2009-12-31 | Oki Data Corporation | Developer, developer container, and image forming apparatus |
US10040959B2 (en) | 2014-06-04 | 2018-08-07 | Hewlett-Packard Development Company, L.P. | Pigment-based inkjet inks |
US10047233B2 (en) | 2014-06-04 | 2018-08-14 | Hewlett-Packard Development Company, L.P. | Magenta inks |
US10294381B2 (en) | 2014-06-04 | 2019-05-21 | Hewlett-Packard Development Company, L.P. | Pigment-based inkjet inks |
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US5998077A (en) * | 1998-06-29 | 1999-12-07 | Xerox Corporation | Coated carrier |
US6066421A (en) * | 1998-10-23 | 2000-05-23 | Julien; Paul C. | Color toner compositions and processes thereof |
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US6562541B2 (en) | 2001-09-24 | 2003-05-13 | Xerox Corporation | Toner processes |
US6899987B2 (en) | 2001-09-24 | 2005-05-31 | Xerox Corporation | Toner processes |
US20060105263A1 (en) * | 2004-11-16 | 2006-05-18 | Xerox Corporation | Toner composition |
US20070025178A1 (en) * | 2005-07-27 | 2007-02-01 | Xerox Corporation | Pigment dispersions and preparation method thereof |
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US7700252B2 (en) | 2006-11-21 | 2010-04-20 | Xerox Corporation | Dual pigment toner compositions |
US20090296173A1 (en) * | 2008-05-28 | 2009-12-03 | Xerox Corporation | Method to create spot colors with white and CMYK toner and achieve color consistency |
US8351100B2 (en) * | 2008-05-28 | 2013-01-08 | Xerox Corporation | Method to create spot colors with white and CMYK toner and achieve color consistency |
US20090325097A1 (en) * | 2008-06-25 | 2009-12-31 | Oki Data Corporation | Developer, developer container, and image forming apparatus |
US8530125B2 (en) * | 2008-06-25 | 2013-09-10 | Oki Data Corporation | Developer, developer container, and image forming apparatus |
US10040959B2 (en) | 2014-06-04 | 2018-08-07 | Hewlett-Packard Development Company, L.P. | Pigment-based inkjet inks |
US10047233B2 (en) | 2014-06-04 | 2018-08-14 | Hewlett-Packard Development Company, L.P. | Magenta inks |
US10294381B2 (en) | 2014-06-04 | 2019-05-21 | Hewlett-Packard Development Company, L.P. | Pigment-based inkjet inks |
US10294382B2 (en) | 2014-06-04 | 2019-05-21 | Hewlett-Packard Development Company, L.P. | Magenta inks |
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